JPH0912695A - Process for producing polyester and copolyester, product produced by the process and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method for preparing a polyester or a copolyester in a simple manner wherein the average molecular weight is high and the molecular weight distribution is narrow and which is non-sticky to allow it to be worked readily.

SOLUTION: A powder polyester is produced by polycondensation of a dicarboxylic acid/diol precondensate (oligomer) in the presence of a polycondensation catalyst that is usually used at a high temperature in a liquid heating medium and as the case may be, in the presence of a co-condensation modifier. The liquid heating medium is inactive, does not have any aromatic atomic group and has a boiling point of 200 to 320°C. The weight ratio of the dicarboxylic acid/diol precondensate (oligomer) to the liquid heating medium is from 20:80 to 80:20 and the polycondensation is carried out at 200 to 320°C in the reaction mixture in the presence of a dispersion stabilizer.

COPYRIGHT: (C)1997,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the production of polyesters and copolyesters by polycondensation of dicarboxylic acid-diol precondensates (oligomers) in the presence of stabilizers in a liquid heat medium at high temperatures of 200 to 320 ° C. On how to do. By this method, fairly high molecular weight products can be prepared under mild conditions. In particular, it is possible to prepare a large amount of a copolymer which has been conventionally obtained only with a low molecular weight and a low melting point.

The invention further relates to the polyesters and copolyesters which can be prepared by this method, and the uses of the polyesters and copolyesters.

[0003]

2. Description of the Prior Art Currently, the most important and most widely produced polyester in the industry is polyethylene terephthalate (hereinafter referred to as "PE" according to the usual term in this specification).
"T"). Modified polyethylene terephthalate (eg, low flammability products) has also been accepted by the textile and technical circles. The method for producing these polyesters generally involves polycondensation in the melt or two-step polycondensation. The two-step polycondensation is carried out in the first step until the average intrinsic viscosity IV in the molten state reaches an appropriate molecular weight corresponding to about 0.5-0.7, and further condensation is carried out in the solid phase. This polycondensation is usually carried out in the presence of known polycondensation catalysts or catalyst systems. The condensation in the solid phase is carried out by heating the polyester chips under reduced pressure or under an inert gas at 180-330 ° C., preferably 220-240 ° C., until the desired molecular weight is reached. However, side reactions may occur along with the polycondensation to break the polyester chain or to generate decomposition products having considerably different properties (for example, a coloring compound or acetaldehyde).

For example, 2,6-naphthalenedicarboxylic acid (abbreviated as "PEN") and / or 4,4'-biphenyldicarboxylic acid (abbreviated as "PEBB") and copolyesters of these dicarboxylic acids (abbreviated as "PENBB"). Starting materials with useful application properties such as) are also described in the literature.

However, since these polyesters are difficult to manufacture, their industrial usefulness is impaired. In the past, it was possible to prepare the desired high molecular weight polyesters exclusively for PEN, PETBB and PENBB at high technical cost.

On the other hand, the high degree of condensation of PEN or PETBB in the molten state has been hindered by the very high viscosity of the product. Such a problem is caused by a co-condensation method in which a starting material is first transesterified at a desired mixing ratio to form an oligomer, and the product is polycondensed, or a mixture condensation method in which a mixture of each oligomer is prepared and polycondensed Or it occurs when preparing a copolyester. When PET / PEN is used, it is difficult to crystallize, and even if an attempt is made to condense in the solid phase to increase the molecular weight, the polyester chips cake and do not work well.

Many proposals have been made regarding methods for producing polyesters.

JP-A-60-139717 discloses a method for producing polyalkylene terephthalate. This method involves heating a suspension of finely divided bis (omega-hydroxyalkyl) terephthalate or an oligomer thereof in a liquid heating medium (eg tetralin) and increasing the temperature to the melting point (eg 2 °
70 ° C.) to disperse the highly polymerized substance in the presence of a condensation catalyst. According to this method, the average particle size is 1
A suspension of 85 μm polyalkylene terephthalate particles is obtained.

A method for producing polyalkylene terephthalate, which is very similar to this, is described in JP-A-60-139717. In this method, for example benzene,
Methyl ethyl ketone or triphenylmethane is used as the heat transfer medium and polystyrene, PVC or polybutadiene as the polymeric additive.

German Patent 2,429,087 discloses a process for producing polymers such as polyesters containing fillers (modifiers) such as TiO ₂ . This method uses BHT (bis (omega-hydroxyalkyl))
A monomer or low molecular weight starting material such as terephthalate) or its oligomer and a filler are polymerized into fine particles at a high temperature in a liquid heating medium (that is, a hydrocarbon or a chlorinated hydrocarbon) in the presence of a specific emulsifier. . For example a hydrocarbon or chlorinated hydrocarbons, aliphatic C _{6- 8} hydrocarbons, aromatic hydrocarbons (e.g. benzene), a methyl benzene or petroleum fractions, aromatic hydrocarbons, carbon tetrachloride, poly chloroethane or mono- -It is recommended to use those containing less than 90% by weight of di- or trichlorobenzene. These can be combined with a polar solvent as needed. The particular emulsifier is a polymer having two different polymer chains (eg, a block polymer of methoxy-polyethylene glycol and glycidyl methacrylate modified poly-12-hydroxystearic acid).

Japanese Patent Publication No. 2707491 discloses a method used for producing polyesters, polyamides and polyesteramides, which is very similar to the above-mentioned production method. In this method, one or more of the starting monomers must not dissolve in the heating medium and the melting point must be above the polymerization temperature. The polymerization is carried out in the presence of a monomer dispersant. The resulting polymer is soluble in the heat carrier and has a molecular chain that can bind to the monomer or polymer particles.

DE-A 2319089 discloses a similar process in which one of the reactants is a solid which is not completely soluble in the heat carrier and the other reactant is soluble in the heat carrier. This reaction is also carried out in the presence of a monomer dispersant, and the resulting polymer has a heat-dissolvable molecular chain component and a molecular chain component capable of binding onto the monomer or polymer particles. The product of this method is a stable polymer dispersion. The molecular weight and acetaldehyde content are not mentioned in this patent publication.

DE-A-1694461 discloses a similar process for preparing a dispersion of synthetic polymer particles in an organic liquid. The condensation of this method is carried out in the presence of a polymerization stabilizer containing a strong polar atomic group that strongly interacts with the polar atomic group of the polymer to be prepared so that the stabilizer has a steric hindrance of 12 angstroms or more on the polymer particle. In a heat medium.

JP-A-63-41528 and JP-A-62-39621 disclose that BHT is condensed into a fine powder type in a heat medium in the presence of a specific dispersant to form PET. doing. Silicone oil is used as the thermal reaction medium. The dispersants used are polysiloxane-vinyl type copolymers such as methacryloyloxypropyl-polyether / methylsiloxane-methylmethacrylate graft polymers and methacryloyloxypropyl-polyether-polydimethylsiloxane.

German Patent Publication Nos. 4117825 and 4226737 disclose polycondensation methods for polyester precondensates. In this method, the initial condensate is polycondensed in a liquid inert heat medium at a temperature equal to or lower than the melting point to produce a polyester having a high average molecular weight and a narrow molecular weight distribution. The heat carrier used is silicone oil or a perfluoroorganic compound (such as perfluoropolyether).

JP-A-62-39621 and JP-A-62-39621.
0-141715 discloses that BHT is condensed into a fine powder type in a heat medium in the presence of a specific dispersant to form PET. Silicone oil is used as the thermal reaction medium. The dispersant used is a graft polymer of a polysiloxane main chain and a polyacrylate side chain, or a acrylate main chain and a siloxane side chain, which are bonded via methacryloyloxypropyl or mercapto.

DE-A-2721501 discloses a process for preparing condensation polymers in a liquid that does not dissolve the product polymer. This method involves polymerizing a starting material in the presence of a reactive polymeric polymer. At least one of the starting materials must be emulsified in a liquid. Reactive polymer has a molecular weight of 1000
It has 20,000 simple chains and has one or more reactive groups capable of participating in condensation polymer formation reactions. This patent publication does not describe a method for preparing a high molecular weight polymer.

US Pat. No. 5,296,586 discloses a method for producing polyesters. In this method, polycondensation is carried out in a boiling inert liquid without adding a dispersion stabilizer. This method produces a polyester mass that is a uniform mass and requires large amounts of relatively inert liquid.

"Polymer", Vol. 33, No. 14, (199)
(2 years) pp. 3066-3072 discloses a method for preparing non-aqueous dispersions of wholly aromatic liquid crystal polymers.
This method uses methyl methacrylate, styrene, acetic acid 2-
Reactants such as 4-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid in the presence of a polymer dispersant such as ethylhexyl and acrylic acid and hydrophobized SiO ₂ are deuterated in a liquid heat medium such as partially hydrogenated terphenyl. It condenses.

The processes described in the prior art for polycondensation in a liquid heating medium are carried out mainly with respect to the production of polymer dispersions or to solve the problems encountered during polycondensation during polymer production. The method of operating with a liquid heat carrier is
Have common advantages. Its advantage is that it avoids the formation of highly viscous reaction mixtures and makes the temperature distribution of the batch more uniform. In general, low molecular weight condensation products such as glycol and water can also be more easily removed from the reaction mixture.
According to this method, a product having a high average molecular weight (that is, a high intrinsic viscosity IV) can be obtained. However, these known methods are not widely applicable. None of the prior art uses these polycondensation processes for copolyester production. Due to the particularly high content of amorofus, there are considerable difficulties in preparation and processing.

A copolyester containing, for example, a desired mol% of 2,6-naphthalene-dicarboxylic acid atomic groups, having a high average molecular weight and being non-adhesive and thus easily processable, is prepared in a simple manner. The way you can do is
It has not been disclosed until now.

Terephthalic acid and about 7-8 mol% of 2,6-
Copolyesters can be prepared from naphthalene-dicarboxylic acids by conventional methods. However, the average molecular weight M _W is only about 15,000-25,000. Chips can be prepared from this polyester,
Further processing of the chips is quite difficult or impossible due to the very high tackiness of the material when heated above the glass transition temperature.

Since the polycondensation melt viscosity is very high,
Polyesters cannot be successfully prepared from 6-naphthalene-dicarboxylic acid. At this time, the condensation can be carried out in the solid phase, but it requires a long reaction time, which increases the preparation cost and promotes the progress of side reactions such as by-products.

[0024]

SUMMARY OF THE INVENTION The present invention provides a simple process for preparing polyesters or copolyesters which have a high average molecular weight, a narrow molecular weight distribution, and are non-sticky and therefore easily processable. It is an object to provide a method capable of doing so. It is also an object to provide polyesters and copolyesters prepared by such a method.

[0025]

Surprisingly, a polyester of desired quality, which could not be prepared by known methods, is surprisingly prepared in a particular non-aqueous heat medium, preferably under defined reaction conditions. by polycondensation at a relatively low polycondensation temperature Te has been found that can be prepared in very high purity with an average molecular weight M _W.

Powdered polyester can be produced by the method of the present invention. d50 value (measure of particle size distribution)
Is less than 2000 μm, preferably less than 1000 μm,
In particular, it is less than 500 μm.

The method of the present invention is more widely applicable than known methods.

The characteristics of the method of the present invention are as follows. -The structure of the device is simpler and there is no need for depressurization or pressurization. -The heat medium is inexpensive. -Dispersion stabilizers are commercially available. -The starting monomer concentration can be increased. If the monomer concentration in the starting mixture is 70% by weight or less, a stable polymer dispersion system can be prepared. -The molecular weight can be increased.・ Reaction time is relatively short.・ Low acetaldehyde content. -The preferred embodiment uses a stirrer of a specific design that distributes nitrogen well in the dispersion (thus further promoting the polycondensation rate and suppressing side reactions),
The diol can be removed even better during polycondensation.

The present invention relates to a dicarboxylic acid-diol precondensate (oligomer) at a high temperature in the presence of a polycondensation catalyst usually used in a liquid heating medium and, where appropriate, a cocondensation modifier. A process for producing a powdered polyester by polycondensation in the presence of a liquid heat carrier, which is inert, has no aromatic groups, and has a boiling point of 200-32.
0 ° C, preferably 220-300 ° C, especially 240-28
5 ° C .; the weight ratio of the dicarboxylic acid-diol initial condensate (oligomer) and the liquid heat medium used is 20: 8.
0 to 80:20, preferably 30:70 to 70: 3
0, especially 50:50 to 70:30; 2 for polycondensation
It relates to a method for producing a powdered polyester, which is carried out in a reaction mixture in the presence of a dispersion stabilizer at 00-320 ° C.

The dicarboxylic acid-diol precondensate used as the starting material in the process of the present invention has the formula: HOOC-A-
One or more dicarboxylic acids represented by COOH and, where appropriate, the hydroxycarboxylic acid HO-A-COOH or a functional derivative thereof, and the formula HO-D-OH, where A and D are divalent organic radicals. ) Is a reaction product with one or more diols. In this reaction, in addition to the reaction product ester, a low polycondensation product (oligomer)
And generally only small amounts of dicarboxylic or hydroxycarboxylic acids or their functional derivatives and diols are present.

Dicarboxylic acid-diol precondensate (oligomer) used in the process of the present invention prepared by the reaction of bis (lower alkyl) dicarboxylic acid and diol.
Having a boiling point of 200-320 ° C., preferably 220-30
It is particularly effective to heat in an inert liquid heating medium which does not have an aromatic atomic group in the technical sense of 0 ° C., particularly 240 to 285 ° C. The weight cost of the dicarboxylic acid-diol initial condensation product (oligomer) and the liquid heat medium used at this time is 2
0:80 to 80:20, preferably 30:70 to 7
It is 0:30, especially 50:50 to 70:30. If appropriate, it is carried out in the presence of dispersion stabilizers and in the presence of known transesterification catalysts. The heating is performed to a temperature at which the lower alkanol liberated during the transesterification reaction can be distilled off. The above-mentioned inert liquid heat medium has no aromatic atomic group in the technical sense. That is, the content of aromatic components in the above-mentioned inert liquid heat medium is 2% by weight or less, preferably 1% by weight or less. Examples of such a heat medium include Isopar P ^™ , Isopar V ^™ , and Exxs.
ol D120 ^™ , Exxsol D140 ^™ , Norp
ar 15 ^™ (manufactured by Exxon Chemical) can be exemplified. A particularly preferable heat medium is an aliphatic hydrocarbon having no aromatic atomic group.

The reaction mixture is heated in the previous reaction phase to about 5 ° C. above the melting point of the dicarboxylic acid bis (lower alkyl) ester.
-50 ° C, preferably 10-40 ° C higher temperature,
The temperature is about 5-50 ° C, preferably 10-40 ° C above the boiling point of the alkanol to be distilled off. in this way,
For the production of the dicarboxylic acid-diol precondensate (oligomer), the same heat medium as used for the polycondensation of the present invention can be particularly preferably used. The method of the present invention comprises:
Starting from the monomeric starting materials, the bis (lower alkyl) dicarboxylic acid alkyl ester and the diol, one proceeds in two sections, the "one-pot processes".
s) ”.

In a particular embodiment of the present invention, the average of the analytical values of the total of all dicarboxylic acid atomic groups is 100 mol%, and 70-100 mol% is represented by the formula: —CO—A ¹ —CO—. Atomic group (I), formula of 0-30 mol%: -CO-
Atomic group represented by A ² -CO- (II), 0-50 mol%
Of the formula: —O—A ³ —CO—, an atomic group (III),
Formula: -O-D ¹ -O- in atomic group represented (IV), and the formula: -O-D ² -O- diol atomic group represented (I
V) or (V) [in the above formula, A ¹ is 1,4-phenylene, 2,6-naphthylene or 4,4′-biphenylene or a desired plural combination thereof, and A ² Is A ¹ having 5 to 16 carbon atoms, preferably 6 to 12 carbon atoms.
Aromatic atomic groups other than, or aromatic aliphatic atomic groups, or C 2-10, preferably 4-8 cyclic or acyclic aliphatic atomic groups, A ³ is 5-12 carbon atoms, It is preferably a 6-10 aromatic atomic group, and D ¹ has 2 carbon atoms.
-4 alkylene or polymethylene, or carbon number 6
-10 cycloalkane or dimethylenecycloalkane, D ² is alkylene or polymethylene having 3-4 carbon atoms, or cycloalkane or dimethylenecycloalkane other than D ¹ having 6-10 carbon atoms, 4-carbon atom
16, preferably a linear addition of the branched alkanediyl 4-8, formula _{- (C 2 H 4 O)} m -C 2 H 4 - an atomic group represented by, m wherein the 1- Is an integer of 40, m is preferably 1 or 2 when the content is 20 mol% or less, and m is preferably 10-40 only when the content is less than 5 mol%]. A dicarboxylic acid-diol precondensate having is used.

The aromatic atomic groups A ² and A ³ are also one or two.
It may have one substituent. The substitutions A ² and A ³ are
It preferably has one substituent. Particularly suitable substituents are C1-4 alkyl, C1-4 alkoxy, chlorine and sulphonic acid.

According to the above, the dicarboxylic acid-diol precondensate used as starting material for the particular embodiment of the process of the invention is one or more, preferably up to 3, in particular 1.
Dicarboxylic acid of one or two formulas: HOOC-A ¹ -COOH and, where appropriate, formula: HOOC-A
^2- COOH represented by dicarboxylic acid or formula: HO-
A hydroxycarboxylic acid represented by A ³ -COOH or a functional derivative of these dicarboxylic acids or hydroxycarboxylic acids and one or more diols represented by the formula: HO-D ¹ -OH and, where appropriate, 1 More than one formula: HO
It is a reaction product with a diol represented by -D ² -OH. In addition to the esters obtained from the starting materials, lower polycondensation products (oligomers) and generally only small amounts of starting materials are also present in the product.

The dicarboxylic acid-diol precondensate (hereinafter also referred to as an oligomer) having the above composition used as a starting material is prepared by first providing a desired ratio of a desired dicarboxylic acid or a functional derivative thereof (for example, a lower alkyl ester). It can be prepared by transesterification with the desired ratio of the desired diols and polycondensation in the specified amount into an oligomer mixture. If appropriate, further condensation is carried out in order to further proceed the oligomerization to the desired degree. When a known suitable catalyst is preferably added using a functional acid derivative, or when a lower alkyl ester (for example, a transesterification catalyst such as a magnesium salt) is used, the reaction between the dicarboxylic acid and the diol does not involve addition of the catalyst. Do without.

However, the dicarboxylic acid-diol precondensate is preferably prepared in a desired composition by a method of mixing each dicarboxylic acid for cocondensation and the desired precondensate of the diol with each other in a desired mixing ratio. be able to. This method has particular technical advantages. That is, transesterification and, if appropriate, oligomerization must be carried out with only a few compounds in the given equimolar ratio. The oligomer composition for the method of the present invention can be easily obtained by simply mixing the respective oligomers prepared for storage.

In order to prepare a copolyester having a predetermined composition by the method of the present invention, it is important to make the composition of the precondensate to be the mol% of the above A ¹ , A ² and A ³ . The polyester prepared according to the present invention is
It will be substantially the same as the mol% of the A ¹ , A ² and A ³ atomic groups of the precondensate used.

Generally, the content of diol in the initial condensate is different from the content of atomic groups IV and V of the polyester finally obtained. When a polyester having a given composition of diol groups is prepared by the method of the present invention, the diol content that must be present in the precondensate to obtain the desired final product is determined by several preliminary tests. Keep it. If the rate of reaction parameters of each diol and the composition of the azeotrope with the heat carrier at that reaction temperature are known, the amount of diol required for the precondensate for the desired polyester composition can be calculated. These parameters are routinely determined but labor-intensive, so preliminary tests can always be done to obtain the final product quickly in practice.

Each compound contained in the initial condensate need not be known in detail in carrying out the method of the present invention.

As mentioned above, a characteristic advantage of the process of the present invention is that many non-tacky solid copolyesters, which could not be obtained by conventional methods, can be prepared with high average molecular weight and in very high yields. It is in. A ¹ is 8-92 mol% 1,4-phenylene and 8-92 mol% 2,6-naphthylene, preferably 16-84 mol% 1,4-phenylene, based on the total amount of atomic groups A ^1. And 16-84 mol% of 2,6-
The process of the invention is particularly advantageous when using naphthylene, especially dicarboxylic acid-diol prepolymers containing 30-70 mol% 1,4-phenylene and 30-70 mol% 2,6-naphthylene.

The process of the invention also has the characteristic advantage that high molecular weight polyesters and copolyesters can be prepared under surprisingly mild reaction conditions in a relatively short time. According to the method of the present invention, it is also possible to prepare a product having a fairly narrow molecular weight distribution in many cases.

The method of the present invention includes a polyester A ¹ are 1,4-phenylene, and uniform or slightly modified is either 2,6-naphthylene or 4,4'-biphenyl, A ¹ is an atomic group 8-92 mol%, preferably 16-84 mol%, especially 30-70 mol%, 1,4-phenylene and 8-92 mol%, preferably 16-84 mol%, based on the total amount of A ¹ . Especially 30-70 mol% of 4,4 '
Applicable to copolyesters prepared using dicarboxylic acid-diol precondensates containing biphenylene.

The advantage is that A ¹ is 8-92 mol%, preferably 16-84 mol%, based on the total amount of atomic groups A ¹ .
In particular, 30-70 mol% 2,6-naphthylene, 8-9
2 mol%, preferably 16-84 mol%, especially 30-7
It also appears when using a dicarboxylic acid-diol precondensate containing 0 mol% 4,4'-biphenylene.

A ¹ contains 1,4-phenylene, 2,6-naphthylene and 4,4'-biphenylene, and the total of 1,4-phenylene and 2,6-naphthylene in A ^{1 is}
The total of 1,4-phenylene and 4,4′-biphenylene or the total of 2,6-naphthylene and 4,4′-biphenylene is 8-92 mol% based on the total amount of atomic group A ¹ , preferably It is also a preferred method of the invention to use 16-84 mol%, especially 30-70 mol% dicarboxylic acid-diol prepolymer.

The process of the present invention comprises a dicarboxylic acid-diol initial stage in which the atomic group of formula III is absent or D ¹ is ethylene, tetramethylene or 1,4-dimethylene-cyclohexane, especially ethylene or tetramethylene. It can be preferably used for polycondensation of a polymer.

Amphiphilic copolymers or surface-modified plate silicates are particularly suitable dispersion stabilizers for the process according to the invention.

The dispersion stabilizer is preferably an amphipathic copolymer or a modified inorganic compound. For example, trialkylammonium salt surface-modified plate silicates, preferably trialkylammonium salt surface-modified bentonite or amphiphilic copolymers of polar polymer units (eg polyvinylpyrrolidone) and non-polar polymer units (eg long chain). (Alpha olefin). The above dispersion stabilizer is 0.01-5.
%, Preferably 0.1-4% by weight.

In a preferred and practical embodiment of the process according to the invention, the starting materials, oligomers, polycondensation catalysts and, where appropriate, further additives are first mixed with a liquid heat carrier and the mixture is heated at an elevated temperature, conveniently. It is heated at 80 ° C. or higher, preferably 130 ° C. or higher, and particularly 160 ° C. or higher to the polycondensation temperature or lower, and the dispersion stabilizer or the dispersion stabilizer mixture and the amphipathic copolymer are added with stirring.

The co-condensable modifiers used in the present invention are two or more ester-forming capable of being inserted into the polyester chain during the polycondensation reaction to impart the desired properties to the polyester. It is a compound having a functional group.
The modifier capable of co-condensing is 15% by weight in the copolycondensation batch.
The following can be present, preferably 10% by weight or less. As a characteristic example of such a co-condensation modifier, a phosphinic acid derivative represented by the following formula can be given.

[0051]

Embedded image In the above formula, R1 is alkylene or polymethylene having 2-6 carbon atoms or phenyl (preferably ethylene). R2 is alkyl, aryl or aralkyl having 1 to 6 carbon atoms (preferably methyl, ethyl, phenyl or o-, m- or p-methylphenyl, especially methyl). Further, a functional derivative represented by the following formula (PHOSPHOLAN ^{™ by} Hoechst AG) can also be used.

[0052]

Embedded image Formulas VIII and IX below:

Embedded image The atomic group represented by is introduced into the copolyester chain by co-condensing these compounds. The copolyester modified in this way has a much lower flammability than the corresponding unmodified copolyester.

As mentioned above, the polycondensation is preferably carried out in a boiling reaction mixture so that the polycondensation product formed is effectively present in the fluid or molten state. Preferably,
The heating to the reaction mixture is such that it boils very vigorously (ie to the extent that the heating medium is observed to reflux considerably). The degree of reflux can be easily adjusted by adjusting the heating temperature.

Low molecular weight reaction products are removed from the polycondensation reaction mixture in a circulating system during this process.

It is particularly advantageous that the low molecular weight reaction products dissolve only in very small amounts in the heating medium used according to the invention. Low molecular weight reaction products precipitate from the distillate,
Form a phase independently. Usually, since it has a high specific gravity, it can be easily separated from the heat medium. When actually separating such immiscible liquids that occur during azeotropic distillation, so-called water separators are used. These devices are generally cylindrical vessels having an upper outlet (also a pressure compensator above the upper outlet if appropriate) and a lower outlet. The lower outlet removes the high specific gravity azeotropic phase,
The upper outlet makes it possible to remove the low specific gravity phase.
The heat separator, which also acts as an entrainer for the azeotrope during distillation, circulates in the reactor and the outlet of the water separator is piped so that the other azeotrope phases can be removed intermittently or continuously. It is connected.

The present invention also relates to the polyesters and copolyesters prepared by the method of the present invention.

Compared with the products prepared according to the prior art, the products prepared according to the process according to the invention have a particularly high purity, in particular a low acetaldehyde content of less than 20 ppm, preferably less than 10 ppm, in particular less than 5 ppm, have very high average molecular weight (M _W), it has a feature of narrow molecular weight distribution. PET and PET
/ PEN copolyester above average molecular weight (GP
Measured by C and expressed in g / mol) is 100,000
Or more, preferably 150,000 or more, particularly 200,0
00 or more. PEN, PENBB, PEBB, PE
In the case of TBB and PENTBB copolyesters, the average molecular weight is 40,000 or higher, preferably 60,000.
Above, especially 80,000 or more. PENTBB is
2,6-naphthalenedicarboxylic acid unit (N), 4,
It is a copolyester (P of poly) containing a 4'-biphenylene dicarboxylic acid unit (BB), a terephthalic acid unit (T) and an ethylene glycol unit (E).

Preferred polyesters of the present invention have a formula of 35-50 mol% based on the total amount of all atomic groups:
Atomic group (I) represented by —CO—A ¹ —CO—, 0-1
5 mol% of formula: —CO—A ² —CO— atomic group (II), 35-50 mol% of formula: —O—D ¹ —O— atomic group (IV), 0-15 mol% of the formula: -O-D ²
Atomic group (V) represented by —O—, formula of 0-25 mol%:
Atomic group represented by ^{-O-A 3 -CO- (III)} , and,
Atomic groups derived from co-condensable modifiers, where appropriate, up to 15% by weight [wherein A ¹ is 1,4-phenylene, 2,6-naphthylene and 4,4′-biphenylene. includes two or more ones of the atomic group, the atomic group included in a ¹ is present at 8 mol% or more based on the total amount of a ^1, a ² is 5-16 carbon atoms, preferably 6- 12 A ¹
Aromatic atomic groups other than, or aromatic aliphatic atomic groups, or C 2-10, preferably 4-8 cyclic or acyclic aliphatic atomic groups, A ³ is 5-12 carbon atoms, It is preferably a 6-10 aromatic atomic group, and D ¹ has 2 carbon atoms.
-4 alkylene or polymethylene, or carbon number 6
-10 cycloalkane or dimethylenecycloalkane, D ² is alkylene or polymethylene having 3-4 carbon atoms, or cycloalkane or dimethylenecycloalkane other than D ¹ having 6-10 carbon atoms, 4-carbon atom
16, preferably a linear addition of the branched alkanediyl 4-8, formula _{- (C 2 H 4 O)} m -C 2 H 4 - an atomic group represented by, m wherein the 1- It is an integer of 40, m is preferably 1 or 2 when the content is 20 mol% or less, and m is limited only when the content is less than 5 mol%.
Is preferably 10-40).

These polyesters and copolyesters of the invention could not be prepared by conventional methods,
Even if it could be prepared, it could only be of poor quality. However, according to the present invention, very good quality polyesters and copolyesters can be obtained.

To date, one group of suitable polyesters of the invention which can be prepared in high quality only by the process of the invention is A ¹
1 of 8-92 mol% but, based on the total amount of atomic A ^1,
4-phenylene and 8-92 mol% 2,6-naphthylene, preferably 16-84 mol% 1,4-phenylene and 16-84 mol% 2,6-naphthylene,
Especially 30-70 mol% of 1,4-phenylene and 30-7
Atomic group I containing 0 mol% 2,6-naphthylene and
Polyesters containing IV and, if appropriate, atomic groups II, III and V.

The particularly high molecular weight polyesters and copolyesters of the invention of high purity and very narrow molecular weight distribution are
A ¹ is either 1,4-phenylene, 2,6-naphthylene or 4,4′-biphenylene, especially A ¹
There 8-92 mole percent based on the total amount of atomic A ^1, 1 preferably of extent of 16 to 84 mol%, in particular 30-70 mol%,
4-phenylene and 8-92 mol%, preferably 16-8
Copolyesters containing 4 mol%, especially 30-70 mol% 4,4'-biphenylene.

[0062] Other suitable polyester, A ^1, based on the total amount of atomic A ¹ 8-92 mol%, preferably 1
A polyester containing 6-84 mol%, especially 30-70 mol% 2,6-naphthylene and 8-92 mol%, preferably 16-84 mol%, especially 30-70 mol% 4,4'-biphenylene. , A ¹ is 1,4-phenylene, 2,
6-naphthylene and 4,4'-biphenylene, which are the total of 1,4-phenylene and 2,6-naphthylene in A ¹ , the total of 1,4-phenylene and 4,4'-biphenylene or 2 , 6-naphthylene and 4,4′-biphenylene based on the total amount of atomic group A ¹ is 8-
92 mol%, preferably 16-84 mol%, especially 30-
The polyester is 70 mol%.

Further preferred copolyesters of the invention are copolyesters having no atomic groups of formula III or copolyesters in which D ¹ is ethylene, tetramethylene or 1,4-dimethylenecyclohexane, especially ethylene or tetramethylene. is there.

The polyesters according to the invention are particularly suitable for coating. For example, it is suitable for powder coating by a dipping process or fluidized bed coating. Generally, it is suitable for powders such as powder fusion type adhesives or binders for compression molding materials, and extrusion molded products such as bottles, films, filanments and fibers for use in the industrial or textile industry.

[0065]

EXAMPLES The present invention will now be described with reference to examples.

Example 1 7 kg of an aliphatic hydrocarbon mixture (ISOPAR V ^™ ) having a boiling point of 275 ° C. or higher was surface-modified in a reactor having a distiller equipped with a feed line, a stirrer, a water separator and a solvent reflux device. Bentonite (BENTONE 38 ^™ ) (120 g) and propylene carbonate (40 g) were stirred vigorously to produce high shear forces in the material. This operation was performed using, for example, Ultra-Turrax. With vigorous stirring, 3 kg of 2,6-naphthalene-dicarboxylic acid / ethylene glycol initial condensate having an average degree of transesterification of 90-100% and 1 g of antimony trioxide were mixed. Then, the mixture was heated and vigorously boiled to obtain a hydrocarbon mixture in which the components were uniformly distributed. The mixture was boiled for 6 hours under continuous stirring under reflux and the distillate obtained was occasionally freed from the glycols which separated in the water separator. The supernatant hydrocarbon mixture in the separator was returned to the reactor. The internal temperature of the reactor in this step was 280 ° C. Samples of the reaction mixture were removed at 1.5 hour intervals to determine the average particle size of the polyester. The following results were obtained. Reaction time (hour) 1.5 3.0 4.5 6.0 Particle size (μm) 16 16 13 17

After the reaction time, the batch was cooled and the polyester produced was separated from the hydrocarbon mixture by filtration, washed, dried and weighed. The yield was 2979 g, 99.3% of theory.

Example 2a (Control of Example 1) For comparison, instead of the hydrocarbon mixture used as the heat carrier in Example 1, an aliphatic mixture (THERMIA E ^™ ) with a boiling point of about 325 ° C-500 ° C was used. ) Was used to repeat Example 1. The reaction temperature was about 280 ° C as in Example 1. During the reaction, the glycol liberated in the condensation reaction mixture was distilled off from the batch, but the heating medium did not boil.

As in Example 1, the polycondensation was stopped after 6 hours and the particle size was measured and found to be 52 μm. After the above post-treatment, 2970 g of polyester were obtained (yield about 99% of theory).

Example 2b (Control of Example 1) For further comparison with the product of Example 1, polyethylene naphthalate was prepared by melt condensation according to the usual procedure. For this purpose, first, 1000 g of dimethyl 2,6-naphthalenedicarboxylate was added to magnesium acetate (I
I) Transesterification was carried out at 200 ° C. with 500 ml of ethylene glycol in the presence of 300 mg of water of crystallization (4 mol) to obtain diglyceryl naphthalenedicarboxylic acid ester and an oligomer. When the separation of methanol was completed, 410 mg of methyl phosphate and 390 antimony trioxide
mg was added to the batch. The melt was polycondensed at 0.1 mbar at 300 ° C. for 3 hours.

The properties of the polyester produced were as shown in the table below.

Example 3 20 kg of 7 kg of an aliphatic hydrocarbon mixture (Isopar P ^™ ) having a boiling point of 240 ° C. or higher is charged in a reactor having a distillator equipped with a feed line, a stirrer, a water separator and a solvent refluxer. % 2,6-naphthalenedicarboxylic acid / ethylene glycol precondensate and a dicarboxylic acid-diol initial mixture containing 80% by weight terephthalic acid / ethylene glycol precondensate were mixed with vigorous stirring. The mixture is heated to an internal temperature of about 260 ° C. and the polyvinylpyrrolidone / polyolefin copolymer (ANTARON V22
0 ^™ ) 140 g.

A homogeneous emulsion of polyester precondensate was formed in the hydrocarbon mixture. While continuing to stir, the mixture was heated to a vigorous boil and the glycol separated in the water separator was occasionally removed from the resulting distillate. The supernatant hydrocarbon mixture was returned to the reactor. The internal temperature of the reactor in this step was about 260 ° C., and this temperature was maintained for 6 hours or more.

After the reaction time had elapsed, the batch was cooled and the polyester produced was separated from the hydrocarbon mixture by filtration, washed with petroleum ether, dried and weighed. The yield was 2960 g, 98.6% of theory.

The amount of heat medium is 3 kg instead of 7 kg, 2
Actually the same results were obtained with kg or 1.3 kg.

Examples 4 and 5 50% by weight of 2,6-naphthalenedicarboxylic acid / ethylene glycol precondensate and 50% by weight of terephthalic acid /
Dicarboxylic acid-diol precondensate containing ethylene glycol precondensate, or 80% by weight of 2,
The batch operation of Example 3 was repeated using a dicarboxylic acid / diol precondensate containing 6-naphthalenedicarboxylic acid / ethylene glycol precondensate and 20 wt% terephthalic acid / ethylene glycol precondensate. The respective yields were 99.1% and 95.8% of the theoretical amount.
The composition of the polyester produced was determined by ¹ H NMR. The results were as shown below.

The molar ratio of the 2,6-naphthalenedicarboxylic acid / terephthalic acid atomic group in the polyester is as follows. Theoretical value 17.27 / 82.72 45.52 / 54.48 76.97 / 23.03 NMR measurement value 13.5 / 86.5 42.2 / 57.8 78.5 / 21.5

Example 6 7 kg of an aliphatic hydrocarbon mixture (ISOPAR P ^™ ) having a boiling point of 240 ° C. or higher was surface-modified in a reactor having a distiller equipped with a feed line, a stirrer, a water separator and a solvent reflux device. Bentonite (BENTONE 38 ^™ ) 210 g and propylene carbonate 40 g were stirred vigorously to create high shear forces in the material. While continuing vigorous stirring, 3 kg of a terephthalic acid / ethylene glycol initial condensate having an average degree of transesterification of 90-100% and 1.2 g of antimony trioxide were mixed. Then, the mixture was heated and vigorously boiled to obtain a hydrocarbon mixture in which the components were uniformly dispersed. While stirring under reflux (internal temperature 260
The mixture was boiled for 6 hours and the distillate obtained was occasionally freed of the glycols separated in a water separator. The supernatant hydrocarbon mixture in the separator was returned to the reactor.

Samples of the reaction mixture were withdrawn at 1.5 hour intervals to determine the average particle size of the polyester. The following results were obtained. Reaction time (hour) 1.5 3.0 4.5 6.0 Particle size (μm) 92 105 125 110

After the reaction time had elapsed, the batch was cooled and the polyester produced was separated from the hydrocarbon mixture by filtration, washed, dried and weighed. Yield is 9 theoretical
9.1%. The properties of the product were as shown in the table below.

Examples 6b, 6c and 6d 1% BENTONE ^™ , ANTARON of the precondensate.
V220 ^™ was used. ISOPAR P as heat carrier
^TM and ISOPAR V ^™ weight ratio 20:80, 50: 5
Used at 0 and 10:90. Reaction temperature and reaction time were as described in Example 6. Products having different molecular weights were obtained depending on the composition of the heating medium. These examples show the effect of the reflux ratio of the heating medium on the molecular weight.

Example 7 (control of Example 6) A heating medium having a boiling point of 355 to 530 ° C. (Sant)
otherm 66 ^TM) was repeated exactly the same procedure as in Example 6 using 7 kg. As in Example 6, the reaction temperature was set to 260 ° C. and maintained for 6 hours. The mixture did not boil under these conditions.

After the reaction time had elapsed, the batch was cooled and the polyester produced was separated from the hydrocarbon mixture by filtration, washed, dried and weighed. Yield is 8 theoretical
2.3%. The properties of the product were as shown in the table below.

Example 8 (Control of Example 6) A further comparison with the product of Example 1 was made. It was prepared by melt-condensing polyethylene terephthalate by a conventional method. At this time, first, dimethyl terephthalate 100
0 g of magnesium (II) acetate (water of crystallization 4 mol) 330
ethylene glycol 600 at 200 ° C in the presence of mg
Transesterification with ml produced terephthalic acid glycol ester and oligomer. When the separation of the methanol was completed, 410 mg of methyl phosphate and 390 mg of antimony trioxide were added to the batch and the molten mixture was adjusted to 0.
Polycondensation was carried out at 280 ° C. for 3 hours at 1 mbar.

The properties of the polyester produced were as shown in the table below.

Example 9 Aliphatic hydrocarbon mixture (Isopar P / Isopar V: volume ratio) having a boiling point of 240 ° C. or higher in a reactor having a distillator equipped with a feed line, a stirrer, a phase separator and a solvent reflux device. 75:25) 29 kg, 2 Antaron V220
33 g of terephthalic acid / ethylene glycol initial condensate was weighed out together with 85 g and 11.1 g of antimony trioxide. 260 to room temperature so that the mixture boils vigorously
Heat to 270 ° C. for 2 hours. The mixture was refluxed for 6 hours (internal temperature 266 ° C.) and the glycol discharged from the distillate was discharged through a phase separator.

The following parameters were determined for the polyesters obtained according to Examples 1-9.

1) Glass transition temperature T _g and crystal melting temperature T _m These parameters were measured by DSC at a heating rate of 10 ° C./min.

2) Specific viscosity V _s (V _s = (t / t ₀ ) -1) This parameter was measured with a solution of 1 g of polyester dissolved in 100 ml of dichloroacetic acid (DCA) at the temperature (° C) shown in the table. . The dissolution time was 90 minutes, and the measurement was performed at 25 ° C.

3) Average molecular weights M _n and M _W These parameters are determined by gel permeation chromatography (GPC) on polystyrene standard polyethylene terephthalate using a hexafluoroisopropanol / chloroform mixture 3:97 (vol%) as mobile phase. It was measured by performing.

4) Particle size (d50 value) This parameter is the MALVERN MASTER-
Span 8 in n-heptane using SIZER X ^™
It was measured by adding 0 ^TM and performing laser light diffraction.

5) Free acetaldehyde content. This parameter is defined as follows: 1 g of polyester powder is used at 140 ° C.
It was measured by performing a gas chromatography vapor void analysis with heating in a closed container for 20 minutes. A helium / acetaldehyde mixture was then used for calibration.

The measurement results obtained are shown in the table below. The column _MW / _Mn = U is also shown in the column of Table 2. Those skilled in the art can know the degree of molecular weight distribution based on this U value.

[0094]

[Table 1]

[0095]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Andre Hentze, Federal Republic of Germany 65719 Hachheim, Nachtigallenweg 4 (72) Inventor, Karsten Blatter, Federal Republic of Germany 65817 Eppstein, Kirchgasse 18

Claims (34)

[Claims] 1. A dicarboxylic acid-diol precondensate (oligomer) in the presence of a polycondensation catalyst usually used in a liquid heating medium at high temperature and, if appropriate, in the presence of a cocondensation modifier. A method for producing a powdery polyester by polycondensation with a liquid heating medium which is inert and does not have an aromatic atomic group, and has a boiling point of 200 to 320 ° C., preferably 220 to 300 ° C.
In particular, the temperature is 240 to 285 ° C., and the weight ratio of the dicarboxylic acid-diol initial condensation product (oligomer) to the liquid heat medium used is 20:80 to 80:
20, preferably 30:70 to 70:30, especially 5
0:50 to 70:30, a method for producing a powdered polyester, wherein polycondensation is carried out at 200-320 ° C. in the presence of a dispersion stabilizer in a reaction mixture. 2. A dicarboxylic acid-diol initial condensation product (oligomer) obtained by the reaction of a dicarboxylic acid bis-lower alkyl ester and a diol is heated in a liquid heat medium, and the liquid heat medium has an aromatic atomic group. No boiling point is 20
0-320 ° C, preferably 220-300 ° C, especially 24
0-285 ° C., and the weight ratio of the dicarboxylic acid-diol initial condensation product (oligomer) to the liquid heat medium used is 20:80 to 80:
20, preferably 30:70 to 70:30, especially 5
0:50 to 70:30, where appropriate in the presence of dispersion stabilizers and in the presence of known transesterification catalysts, to a temperature at which the lower alkanol liberated during transesterification can be distilled off. The method of claim 1. 3. The sum of all dicarboxylic acid atomic groups is 10
The analysis group average value was 0 mol%, and 70-100 mol% of the atomic group (I) represented by the formula: —CO—A ¹ —CO—, 0
-30 mol% of the formula: -CO-A ² -CO- in atomic group represented (II), 0-50 mol% of the formula: -O-A ³ -CO-
An atomic group (III) represented by the formula: diol atomic group (IV) represented by the formula: -O-D ¹ -O- and the formula: -O-D ² -O-
And (V) (in the above formula, A ¹ is 1,4-phenylene, 2,6-naphthylene, or 4,4′-biphenylene or a desired plural combination thereof, and A ² is Aromatic atomic group or aromatic aliphatic atomic group other than A ¹ having 5 to 16 carbon atoms, preferably 6 to 12, or cyclic or acyclic aliphatic atom having 2 to 10 carbon atoms, preferably 4 to 8 carbon atoms Group, A ³ is an aromatic atomic group having 5 to 12 carbon atoms, preferably 6 to 10, D ¹ is alkylene or polymethylene having 2 to 4 carbon atoms, or cycloalkane having 6 to 10 carbon atoms Or dimethylene cycloalkane, D ² is alkylene or polymethylene having 3-4 carbon atoms, or cycloalkane or dimethylenecycloalkane other than D ¹ having 6-10 carbon atoms, 4-16 carbon atoms, preferably 4 − Linear addition of branched alkanediyl, formula _{- (C 2 H 4 O)} m -C 2 H 4 - an atomic group represented by, m wherein is an integer of 1-40, containing When the amount is 20 mol% or less, m is preferably 1 or 2
And a dicarboxylic acid-diol precondensate having a content of less than 5 mol% and m is preferably 10-40) is used. 4. A ¹ is 8-based on the total amount of atomic groups A ^1.
4. The method of any of claims 1-3, wherein a dicarboxylic acid-diol prepolymer containing 92 mol% 1,4-phenylene and 8-92 mol% 2,6-naphthylene is used. 5. A ¹ is 16 based on the total amount of atomic groups A ^1.
-84 mol% 1,4-phenylene and 16-84 mol%
The method according to claim 1, wherein the dicarboxylic acid-diol prepolymer containing 2,6-naphthylene is used. 6. A ¹ is 30 based on the total amount of atomic groups A ^1.
-70 mol% 1,4-phenylene and 30-70 mol%
The method according to claim 1, wherein the dicarboxylic acid-diol prepolymer containing 2,6-naphthylene is used. 7. A ¹ is 8-based on the total amount of atomic groups A ^1.
Using a dicarboxylic acid-diol prepolymer containing 92 mol%, preferably 16-84 mol% 1,4-phenylene and 8-92 mol%, preferably 16-84 mol% 4,4′-biphenylene, The method according to claim 1. 8. A ¹ is 8-based on the total amount of atomic groups A ^1.
Using a dicarboxylic acid-diol prepolymer containing 92 mol%, preferably 16-84 mol% 2,6-naphthylene and 8-92 mol%, preferably 16-84 mol% 4,4'-biphenylene, The method according to claim 1. 9. A ¹ includes 1,4-phenylene, 2,6-naphthylene and 4,4′-biphenylene, and the total of 1,4-phenylene and 2,6-naphthylene in A ^{1 is}
The total of 1,4-phenylene and 4,4′-biphenylene or the total of 2,6-naphthylene and 4,4′-biphenylene is 8-92 mol% based on the total amount of atomic group A ¹ , preferably 16-84 mol% dicarboxylic acid-
9. The method of any of claims 1-8, wherein a diol prepolymer is used. 10. A dicarboxylic acid-diol precondensate having no atomic group represented by formula III is used.
9. Any of the nine methods. 11. The method according to claim 1, wherein a dicarboxylic acid-diol prepolymer in which D ¹ is ethylene, tetramethylene or 1,4-dimethylenecyclohexane is used. 12. The method according to claim 1, wherein a dicarboxylic acid-diol prepolymer in which D ¹ is ethylene or tetramethylene is used. 13. The method according to claim 1, wherein the dispersion stabilizer is an amphipathic copolymer or a surface-modified plate silicate, and is used at 0.01-5% by weight. 14. The method according to claim 1, wherein the dispersion stabilizer is a plate silicate surface-modified with a trialkylammonium salt, preferably bentonite surface-modified with a trialkylammonium salt. 15. The method of any of claims 1-14, wherein the dispersion stabilizer is an amphipathic copolymer of polar polymer units such as polyvinylpyrrolidone or non-polar polymer units such as long chain alpha-olefins. 16. The starting materials, oligomers, polycondensation catalyst and, if appropriate, further additives are first mixed with a liquid heating medium, and the mixture is heated to a high temperature, conveniently above 80 ° C., preferably above 130 ° C., especially at 160 ° C. The method according to any one of claims 1 to 15, wherein the dispersion stabilizer or the dispersion stabilizer mixture is stirred and added at a temperature of not less than ° C and not more than the polycondensation temperature, and the mixture is stirred. 17. A process according to any of claims 1-16, wherein the polycondensation is carried out in a boiling reaction mixture. 18. The method according to claim 1, wherein the heat carrier is an aliphatic hydrocarbon having an aromatic content of 2% by weight or less. 19. The method of any of claims 1-18, wherein the heat transfer medium is an aliphatic hydrocarbon. 20. The method according to any one of claims 1-19, wherein low molecular weight reaction products are removed from the polycondensation reaction into the circulation system. 21. A polyester or copolyester produced by the method of claim 1. 22. The polyester or copolyester of claim 21, wherein A ¹ is ^one of 1,4-phenylene, 2,6-naphthylene or 4,4′-biphenyl. 23. All polyester atomic groups (I)-
35-50 mol% formula based on the total amount of (V):-
Atomic group (I) represented by CO-A ¹ -CO-, 0-15
Mol% of formula: —CO—A ² —CO— atomic group (I
I), 35-50 mol% of the formula: —O—D ¹ —O—, an atomic group (IV), 0-15 mol% of the formula: —O—D ² —O
Atomic group (V) represented by-, formula of 0-25 mol%: -O
Atomic group (III) represented by —A ³ —CO— and, if appropriate, an atomic group derived from a modifier capable of cocondensation of 15% by weight or less (in the above formula, A ¹ is 1 , 4-phenylene, 2,6-naphthylene and 4,4' includes two or more atomic groups of the biphenylene, each atomic group included in a ¹ is 8 mol% or more based on the total amount of a ¹ And A ² is an aromatic atomic group or aromatic aliphatic atomic group other than A ¹ having 5-16 carbon atoms, preferably 6-12, or a ring having 2-10 carbon atoms, preferably 4-8 carbon atoms. A cyclic or acyclic aliphatic atomic group, A ³ is an aromatic atomic group having 5 to 12 carbon atoms, preferably 6 to 10, D ¹ is alkylene or polymethylene having 2 to 4 carbon atoms, or a cycloalkane or dimethylene cycloalkane 6-10 carbon atoms, D ² are carbon 3-4 alkylene or polymethylene or D ¹ other cycloalkane or dimethylene cycloalkane having a carbon number 6-10, 4-16 carbon atoms, preferably a linear addition of the branched alkanediyl 4-8, wherein _{- (C 2 H 4 O)} m -C 2 H 4 - an atomic group represented by a m is an integer of 1-40 wherein the m when the content is less than 20 mol% Preferably 1 or 2
And m is preferably 10-40 only if the content is less than 5 mol%). 24. A ¹ is 8 based on the total amount of atomic groups A ^1.
3. Containing atomic groups I and IV containing -92 mol% 1,4-phenylene and 8-92 mol% 2,6-naphthylene, and, where appropriate, atomic groups II, III and V.
3 polyester or copolyester. 25. A ^1, based on the total amount of atomic A ¹ 1
A compound containing atomic groups I and IV containing 6-84 mol% 1,4-phenylene and 16-84 mol% 2,6-naphthylene, and where appropriate atomic groups II, III and V. 23 or 24 polyester or copolyester. 26. A ¹ is 3 based on the total amount of atomic groups A ^1.
A compound comprising atomic groups I and IV containing 0-70 mol% 1,4-phenylene and 30-70 mol% 2,6-naphthylene, and where appropriate atomic groups II, III and V. A polyester or copolyester of any of 23-25. 27. A ¹ is 8 based on the total amount of atomic groups A ^1.
-92 mol%, preferably 16-84 mol% 1,4-
Atomic group I containing phenylene and 8-92 mol%, preferably 16-84 mol% 4,4′-biphenylene and
A polyester or copolyester according to any of claims 23 to 26, comprising IV and, where appropriate, atomic groups II, III and V. 28. A ¹ is 8 based on the total amount of atomic groups A ^1.
-92 mol%, preferably 16-84 mol%, especially 30
-70 mol% 2,6-naphthylene and 8-92 mol%,
23. Preferably comprising atomic groups I and IV and, where appropriate, atomic groups II, III and V, comprising 16-84 mol%, especially 30-70 mol% 4,4'-biphenylene. Polyester or copolyester of any of 27. 29. A ¹ includes 1,4-phenylene, 2,6-naphthylene and 4,4′-biphenylene, and 1,4
-The sum of phenylene and 2,6-naphthylene, 1,4-
The total of phenylene and 4,4′-biphenylene or the total of 2,6-naphthylene and 4,4′-biphenylene is 8-92 mol% based on the total amount of atomic group A ¹ , preferably 16-84 mol %, Especially 30-70 mol%, including atomic groups I and IV, where appropriate atomic group II,
The polyester or copolyester of any of claims 23-28 comprising III and V. 30. The atomic group represented by the formula III does not exist,
A polyester or copolyester according to any of claims 23-29. 31. Atomic groups I and IV, where D ¹ is ethylene, tetramethylene or 1,4-dimethylene-cyclohexane, preferably ethylene or tetramethylene, and where appropriate atomic groups II, III and V. A polyester or copolyester according to any of claims 23-30, comprising: 32. Use of a polyester or copolyester according to any of claims 20-31 for coating, in particular for powder coating by dipping or fluidized bed coating. 33. Use of the polyester or copolyester according to any one of claims 20 to 31 as a powder melt adhesive or a builder for compression molding materials. 34. Use of a polyester or copolyester according to any of claims 20-31 for the production of extruded articles such as bottles, films or filaments for use in the industrial or textile industry.